Modular Functionalization of Electrodes by Cross‐Coupling Reactions at Their Surfaces

Due to the increasing importance of modified electrodes for many applications in nanotechnology, including molecular electronics, bioelectronics, and sensors, there is a need to find ways to chemically attach suitable molecular films onto the electrodes. Combining the electroreduction of aryl diazonium salts with the Sonogashira cross‐coupling reaction, a new modular technique to modify electrodes is presented. The new technique allows a wide range of functional groups to be introduced onto electrode surfaces with high surface coverage by the functional subunit. Various organic subunits, including redox chromophores, are successfully attached to platinum electrodes. The corresponding films are characterized using cyclic voltammetry, X‐ray photoelectron spectroscopy, atomic force microscopy, and contact‐angle measurements. The electroreduction of diazonium salts is successfully achieved on a broad variety of conducting and semiconducting surfaces, which shows that the technique is applicable to a broad variety of substrates.